WO2018207728A1 - ポリアミド微粒子の製造方法およびポリアミド微粒子 - Google Patents

ポリアミド微粒子の製造方法およびポリアミド微粒子 Download PDF

Info

Publication number
WO2018207728A1
WO2018207728A1 PCT/JP2018/017616 JP2018017616W WO2018207728A1 WO 2018207728 A1 WO2018207728 A1 WO 2018207728A1 JP 2018017616 W JP2018017616 W JP 2018017616W WO 2018207728 A1 WO2018207728 A1 WO 2018207728A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
fine particles
polymer
polymerization
polyamide fine
Prior art date
Application number
PCT/JP2018/017616
Other languages
English (en)
French (fr)
Japanese (ja)
Other versions
WO2018207728A9 (ja
Inventor
浅野到
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to US16/606,837 priority Critical patent/US11485822B2/en
Priority to CN201880030995.2A priority patent/CN110612320B/zh
Priority to KR1020197029952A priority patent/KR102538062B1/ko
Priority to RU2019140599A priority patent/RU2771710C2/ru
Priority to EP18798029.7A priority patent/EP3623411A4/en
Priority to JP2018525495A priority patent/JP6558498B2/ja
Publication of WO2018207728A1 publication Critical patent/WO2018207728A1/ja
Publication of WO2018207728A9 publication Critical patent/WO2018207728A9/ja
Priority to US17/955,169 priority patent/US11807717B2/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/46—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating

Definitions

  • the present invention relates to a method for producing polyamide fine particles by a simple method and a polyamide fine particle comprising a polyamide having a high crystallization temperature, a smooth surface, a narrow particle size distribution, and a high sphericity.
  • Polyamide fine particles are used for various applications such as powder coatings, taking advantage of the characteristics of high toughness, flexibility and high heat resistance.
  • the solid and smooth surface polyamide 12 fine particles made of polyamide 12 and having no pores in the inside give a good touch feeling derived from the smooth surface shape in addition to the flexibility of the resin itself. It is possible and used for high quality cosmetics and paint applications.
  • polyamide resins having higher crystallization temperatures such as polyamide 6 and polyamide 66, have higher versatility and melting point than polyamide 12, and may be widely used for higher heat resistance applications. Porous fine particles and fine particles with a wide particle size distribution are produced.
  • polyamide 6 fine particles for example, there is a method in which a polyamide 6 is dissolved in a solvent and then a non-solvent and water are added to produce porous polyamide 6 fine particles (Patent Documents 1 and 2). Further, there are a method in which polyamide is strongly stirred in a medium such as polyethylene glycol at a temperature higher than the melting point, and a method in which a polyamide raw material is subjected to a polycondensation reaction in a silicone oil medium (Patent Documents 3 and 4). As another method, an anionic polymerization is performed in a paraffin medium to provide amorphous polyamide 6 fine particles (Patent Document 5).
  • Patent Document 6 JP 2002-80629 A JP 2010-053272 A JP 60-040134 A JP 10-316750 A JP 61-181826 A Japanese Patent Application Laid-Open No. 08-073602
  • Patent Documents 1 and 2 reduce the solubility in a solvent and precipitate polyamide, so that porous fine particles are produced.
  • An object of the present invention is to obtain a polyamide fine particle having a high method of producing polyamide fine particles by a simple method, and further comprising a polyamide having a high crystallization temperature, a smooth surface, a narrow particle size distribution, and a high sphericity.
  • the method for producing polyamide fine particles of the present invention has the following constitution. That is, A method for producing polyamide fine particles by polymerizing a polyamide monomer (A) in the presence of the polymer (B) at a temperature equal to or higher than the crystallization temperature of the obtained polyamide, A method for producing polyamide fine particles in which a polymer (B) is uniformly dissolved and polyamide fine particles are precipitated after polymerization.
  • the polyamide fine particles of the present invention have the following configuration. That is, Polyamide fine particles having a number average particle size of 0.1 to 100 ⁇ m, a sphericity of 90 or more, a particle size distribution index of 3.0 or less, a linseed oil absorption of 100 mL / 100 g or less, and a crystallization temperature of 150 ° C. or more, It is.
  • polyamide fine particles of the present invention it is preferable to produce polyamide fine particles in the presence of a solvent (C) of the monomer (A) and the polymer (B).
  • the square of the solubility parameter difference between the monomer (A) and the polymer (B) is 0.1 to 25, and the square of the solubility parameter difference between the polyamide and the polymer (B) is 0.
  • a range of 1 to 16 is preferable.
  • the solvent (C) is preferably water.
  • the polymer (B) preferably has no polar group or has one selected from a hydroxyl group and a hydroxyl group.
  • the polymer (B) is preferably polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymer, and alkyl ethers thereof.
  • the molecular weight of the polymer (B) is preferably 500 to 500,000.
  • the polyamide constituting the polyamide fine particles is preferably any one selected from polyamide 6, polyamide 66, and copolymers thereof.
  • the polyamide constituting the polyamide fine particles preferably has a weight average molecular weight of 8,000 or more.
  • the production method of the present invention it is possible to produce a polyamide having a high crystallization temperature as a fine sphere with a spherical shape and a smooth surface by a safe and simple method.
  • the polyamide fine particles have a spherical and smooth surface with a narrow particle size distribution, and thus have a slippery property.
  • the heat resistance derived from a high crystallization temperature, a spherical and smooth surface form, and a uniform particle diameter can be applied to highly functional paints such as severe conditions that cannot be used conventionally.
  • the amide group concentration in the polyamide is increased, so that the moisture retention is increased, and it is possible to achieve both a smooth and uniform feel and a moist feeling due to the true spherical shape and uniform particle size.
  • FIG. 2 is a scanning electron micrograph of polyamide fine particles obtained in Example 1.
  • FIG. 3 is a scanning electron micrograph of polyamide fine particles obtained in Example 2.
  • FIG. 2 is a scanning electron micrograph of polyamide fine particles obtained in Example 8.
  • FIG. 2 is a scanning electron micrograph of polyamide fine particles obtained in Example 10.
  • FIG. 4 is a scanning electron micrograph of polyamide fine particles obtained in Comparative Example 3.
  • the present invention produces polyamide fine particles by polymerizing a polyamide monomer (A) in the presence of the polymer (B) at a temperature higher than the crystallization temperature of the polyamide obtained by polymerizing the monomer (A).
  • the polyamide monomer (A) and the polymer (B) are uniformly dissolved at the start of polymerization, and the polyamide fine particles are precipitated after the polymerization.
  • a polyamide having a high melting point and a higher melting point is also characterized by the fact that polyamide particles can be obtained that are spherical, smooth, fine and have a narrow particle size distribution.
  • the polyamide monomer (A) at the start of polymerization is uniformly dissolved in the polymer (B) may be confirmed by visual observation that the reaction vessel is a transparent solution. When it is in a state of being separated into a suspension or two phases at the start of polymerization, it indicates that the polyamide monomer (A) and the polymer (B) are incompatible with each other. Become. In this case, polymerization may be started after the solvent (C) is further used to homogenize the polyamide monomer (A) and the polymer (B). Whether or not the polyamide fine particles are precipitated after the polymerization may be confirmed by visual observation that the reaction tank is a suspension. A homogeneous solution at the end of the polymerization indicates that the polyamide and the polymer (B) are uniformly compatible, and aggregates and porous fine particles are formed by cooling or the like.
  • the polyamide constituting the polyamide fine particles of the present invention refers to a polymer having a structure containing an amide group, and includes a polycondensation reaction of amino acids as polyamide monomers (A), anionic ring-opening polymerization using lactams and an initiator, cation It is produced by ring-opening polymerization or ring-opening polymerization after hydrolysis with water, polycondensation reaction of dicarboxylic acid and diamine, or salts thereof.
  • lactams a uniform solution with the monomer (A) or the polymer (B) is not formed by the initiator, and the initiator is ignitable, so that it is easy to obtain true spherical and smooth polyamide particles.
  • polyamide monomer (A) used as a raw material for the polyamide fine particles in the production method of the present invention include amino acids such as aminohexanoic acid, aminoundecanoic acid, aminododecanoic acid, paramethylbenzoic acid, and ⁇ -caprolactam.
  • Lactams such as lauric acid, oxalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1, Dicarboxylic acids such as 3-cyclohexanedicarboxylic acid and ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, From diamines such as decanediamine, dodecanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane and 3,3'-dimethyl-4,
  • Two or more of these monomers (A) may be used as long as they do not impair the present invention, and other monomers capable of copolymerization may be included.
  • Aminohexanoic acid, ⁇ -caprolactam, hexamethylenediamine, and the like are obtained because the solubility of the monomer (A) and the polymer (B) is improved and the resulting polyamide fine particles have a fine particle size and a narrow particle size distribution.
  • Adipic acid is preferred, aminohexanoic acid and ⁇ -caprolactam are more preferred, and ⁇ -caprolactam is most preferred.
  • polyamide produced by polymerizing the monomer (A) include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide ( Polyamide 46), polytetramethylene sebacamide (polyamide 410), polypentamethylene adipamide (polyamide 56), polypentamethylene sebacamide (polyamide 510), polyhexamethylene sebacamide (polyamide 610), polyhexa Methylenedodecanamide (polyamide 612), polydecane methylene adipamide (polyamide 106), polydodecamethylene adipamide (polyamide 126), polydecane methylene sebamide (polyamide 1010), liundecanamide (polyamide 11), poly Dodecamide (Polyamide) 12), polyhexamethylene terephthalamide (polyamide 6T), polydecamethylene terephthalamide (polyamide 10T), polycaproamide / poly
  • the crystallization temperature is 150 ° C. or higher. It is preferable that it is any one selected from polyamide 6, polyamide 66 and copolymers thereof.
  • the range of the weight average molecular weight of the polyamide constituting the polyamide fine particles is preferably 8,000 to 3,000,000. From the viewpoint of inducing phase separation with the polymer (B), the weight average molecular weight is more preferably 10,000 or more, further preferably 15,000 or more, and most preferably 20,000 or more. In the present invention, since the viscosity during polymerization depends on the polymer (B), an increase in viscosity due to an increase in the molecular weight of the polyamide is suppressed. Therefore, there is an advantage that the polymerization time of the polyamide can be extended and the molecular weight can be extremely increased.
  • the weight average molecular weight of the polyamide is more preferably 2,000,000 or less. The following is more preferable.
  • the weight average molecular weight of the polyamide constituting the polyamide fine particles indicates a weight average molecular weight obtained by converting the value measured by gel permeation chromatography using hexafluoroisopropanol as a solvent and converted to polymethyl methacrylate.
  • the polymer (B) in the present invention refers to a polymer that dissolves in the polyamide monomer (A) at the start of polymerization but is incompatible with the polyamide after polymerization. Dissolution is judged by whether or not the polymer (B) and the monomer (A) are uniformly dissolved under conditions of temperature and pressure at which polymerization is initiated. The incompatibility between the polymer (B) and the polyamide is determined by whether the polymer (B) is separated into a suspension or two phases under the conditions of temperature and pressure after polymerization. Judgment as to whether the solution is a homogeneous solution, suspension, or two-phase separation can be made by visually checking the reaction vessel.
  • the polymer (B) is preferably non-reactive with the polyamide monomer from the viewpoint of precipitating the polyamide fine particles from a uniform solution.
  • the polymer (B) does not have a polar group that reacts with a carboxyl group or amino group that forms an amide group of polyamide, or has a polar group that has low reactivity with the carboxyl group or amino group.
  • Examples of polar groups that react with carboxyl groups and amino groups include amino groups, carboxyl groups, epoxy groups, and isocyanate groups.
  • Examples of the polar group having low reactivity with a carboxyl group or an amino group include a hydroxyl group and a hydroxyl group. From the viewpoint of suppressing a crosslinking reaction, these have 4 or less polar groups in the polymer (B).
  • the polymer (B) is incompatible with polyamide from the viewpoint of making the fine particles of the polyamide fine and the solubility in the monomer (A) and narrowing the particle size distribution, but it has an affinity. Higher is preferable.
  • the affinity between the monomer (A) / polymer (B) and between the polymer (B) / polyamide is based on the solubility parameters (hereinafter referred to as SP values) of ⁇ A , ⁇ B , ⁇ PA (J 1 / 2 / cm 3/2 ), the square of the solubility parameter difference between the monomer (A) and the polymer (B), that is, ( ⁇ A ⁇ B ) 2 , the polymer (B) and the polyamide
  • the interval can be expressed by the square of the difference in solubility parameter, that is, ( ⁇ PA ⁇ B ) 2 .
  • ( ⁇ A ⁇ B ) 2 preferably satisfies the range of 0.1 to 25.
  • the lower limit of ( ⁇ A ⁇ B ) 2 is more preferably 0.3 or more, further preferably 0.5 or more, and particularly preferably 1 or more.
  • the upper limit of ( ⁇ A ⁇ B ) 2 is more preferably 16 or less, further preferably 12 or less, particularly preferably 10 or less, and most preferably 7 or less.
  • ( ⁇ PA ⁇ B ) 2 preferably satisfies the range of 0.1 to 16.
  • the lower limit of ( ⁇ PA ⁇ B ) 2 is more preferably 0.3 or more, further preferably 0.5 or more, and particularly preferably 1 or more.
  • the upper limit of ( ⁇ PA ⁇ B ) 2 is more preferably 12 or less, further preferably 10 or less, particularly preferably 7 or less, and most preferably 4 or less.
  • the SP value is Properties of Polymers 4th Edition (written by DW Van Krevelen, published by Elsevier Science 2009), Chapter 7 and P215. .
  • a value calculated from the cohesive energy density of Fedors described in the same chapter P195 and the molar molecular volume is shown.
  • the value which added the product of each SP value and molar fraction is shown.
  • polymers (B) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol-polytetramethylene glycol. Copolymerization and hydroxyl groups at one end or both ends were blocked with methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, etc.
  • alkyl ethers examples thereof include alkyl ethers, alkylphenyl ethers blocked with octylphenyl groups, and the like.
  • polyethylene glycol polyethylene glycol-polypropylene glycol copolymer, polypropylene glycol, polytetramethylene glycol, and These alkyl ethers are preferred, and from the standpoint of excellent compatibility with water used as a solvent for ring-opening polymerization by hydrolysis of the polyamide monomer (A) and polyethylene glycol, polyethylene glycol-polypropylene glycol copolymer.
  • a polymer is more preferred, and polyethylene glycol is most preferred. You may use 2 or more types of these simultaneously in the range which does not impair this invention.
  • the weight average molecular weight of the polymer (B) is preferred from the viewpoint of preventing the viscosity of the uniform solution from becoming too high and extremely slowing the polymerization reaction of the polyamide.
  • the upper limit is 500,000, more preferably 100,000 or less, and even more preferably 50,000 or less.
  • the weight average molecular weight of the polymer (B) is preferably 500 or more, more preferably 1,000 or more. Preferably, 2,000 or more is more preferable.
  • the weight average molecular weight of the polymer (B) indicates a weight average molecular weight obtained by converting a value measured by gel permeation chromatography using water as a solvent into polyethylene glycol.
  • the value measured by gel permeation chromatography using tetrahydrofuran as a solvent is a weight average molecular weight converted to polystyrene.
  • the polymerization is started at a temperature higher than the crystallization temperature of the polyamide obtained by polymerizing the monomer (A). Produces fine particles.
  • the polyamide fine particles are homogeneously induced without crystallizing, so that after the polymerization, spheres, surface smoothness, fineness and narrow particle size distribution are obtained. It is considered that polyamide fine particles are precipitated.
  • the mass ratio of the monomer (A) and the polymer (B) when polymerizing is preferably in the range of 5/95 to 80/20.
  • the lower limit of the mass ratio of monomer (A) / polymer (B) is more preferably 10/90, still more preferably 20/80, and most preferably 30/70.
  • the upper limit of the mass ratio of monomer (A) / polymer (B) is more preferably 70/30, further preferably 60/40, and particularly preferably 50/50.
  • a known method can be used as a method for polymerizing the monomer (A) into polyamide.
  • the method depends on the type of monomer (A), but in the case of lactams, anionic ring-opening polymerization using an alkali metal such as sodium or potassium or an organometallic compound such as butyllithium or butylmagnesium as an initiator, In general, cationic ring-opening polymerization using an acid as an initiator, hydrolyzing-type ring-opening polymerization using water, or the like is generally used.
  • cationic ring-opening polymerization or hydrolytic ring-opening polymerization is preferable.
  • hydrolysis-type ring-opening polymerization is more preferable from the viewpoint of suppressing the coloring of the polyamide by the initiator and the gelation or decomposition reaction due to the crosslinking reaction.
  • the method for ring-opening polymerization of lactams by hydrolysis is not limited as long as it is a known method, but pressurizing in the presence of water to generate amino acids while promoting lactam hydrolysis, and then removing water.
  • a method of performing ring-opening polymerization and polycondensation reaction is preferable.
  • the amount of water to be used is not particularly limited as long as the hydrolysis of the lactam proceeds, but if the total amount of the monomer (A) and the polymer (B) is usually 100 parts by mass, the use of water The amount is preferably 100 parts by mass or less. In order to improve the production efficiency of the polyamide fine particles, the amount of water used is more preferably 70 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
  • the lower limit of the amount of water used is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more.
  • a known method such as a method of removing while flowing an inert gas such as nitrogen at normal pressure or a method of removing under reduced pressure is appropriately used. it can.
  • the monomer (A) is an amino acid, dicarboxylic acid and diamine, or a salt thereof
  • a polycondensation reaction can be used as a polymerization method.
  • these monomers (A) there are combinations that do not dissolve uniformly with the polymer (B).
  • solvent (C) of monomer (A) and polymer (B). it is possible to produce polyamide fine particles by further adding solvent (C) of monomer (A) and polymer (B).
  • Solvent (C) is not particularly limited as long as it is in the above range, but it is necessary to dissolve monomer (A) and polymer (B) and to be discharged out of the system in order to advance the polycondensation reaction. Water is most preferred because it is identical to water.
  • the polymer By adding polyethylene glycol, polyethylene glycol-polypropylene glycol copolymers as B), and their alkyl ethers and water as solvent (C), a uniform solution is formed at the temperature at which polymerization is initiated. Thereafter, the condensed water generated by the progress of the polycondensation with the water of the solvent (C) is discharged out of the reaction tank, so that the polyamide fine particles can be produced while the polymerization proceeds.
  • an amino acid such as aminohexanoic acid or aminododecanoic acid
  • a dicarboxylic acid such as adipic acid and hexamethylenediamine and a diamine
  • the amount of water used as the solvent (C) is preferably 10 to 200 parts by mass. From the viewpoint of preventing the particle diameter from becoming coarse, the amount of water used is more preferably 150 parts by mass or less, and still more preferably 120 parts by mass or less. On the other hand, from the viewpoint of ensuring that it functions as a solvent, the amount of water used is preferably 20 parts by mass or more, and more preferably 40 parts by mass or more.
  • lactams and amino acids and / or dicarboxylic acids or diamines may be used as a mixture of two or more.
  • water functions as a hydrolysis or a solvent (C).
  • the polymerization temperature is not particularly limited as long as the polymerization of the polyamide proceeds, but from the viewpoint of controlling the high crystallization temperature of the polyamide closer to a true sphere and having a smooth surface, the polymerization temperature can be obtained. It is preferable that the temperature be equal to or higher than the crystallization temperature.
  • the polymerization temperature is more preferably the crystallization temperature of the obtained polyamide + 15 ° C. or more, more preferably the crystallization temperature of the obtained polyamide + 30 ° C. or more, and the crystallization temperature of the obtained polyamide + 45 ° C. or more. Is particularly preferred.
  • the polymerization temperature is preferably set to the melting point of the obtained polyamide + 100 ° C. or lower. + 50 ° C. or lower is more preferable, the melting point of the obtained polyamide is more preferably + 20 ° C. or lower, polymerization at the same temperature as the melting point of the obtained polyamide is particularly preferable, and the melting point of the obtained polyamide is ⁇ 10 ° C. or lower. Most preferably.
  • the crystallization temperature of the polyamide constituting the polyamide fine particles is a DSC method, and the temperature is increased at a rate of 20 ° C./minute from 30 ° C. to an endothermic peak showing the melting point of the polyamide at a temperature of 30 ° C. in a nitrogen atmosphere.
  • the peak of the exothermic peak that appears when the temperature is cooled to 30 ° C. at a rate of 20 ° C./min after holding for 1 minute is shown. Further, the peak of the endothermic peak when the temperature is further raised at 20 ° C./min after cooling is defined as the melting point of the polyamide fine particles.
  • the polymerization time can be adjusted as appropriate according to the molecular weight of the polyamide fine particles to be obtained. On the other hand, it is ensured that the polymerization proceeds and the polyamide fine particles are obtained. From the viewpoint of preventing progress such as deterioration of the polymer and (B), it is usually preferably in the range of 0.1 to 70 hours. As a minimum of polymerization time, 0.2 hours or more are more preferred, 0.3 hours or more are still more preferred, and 0.5 hours or more are especially preferred. The upper limit of the polymerization time is more preferably 50 hours or less, further preferably 25 hours or less, and particularly preferably 10 hours or less.
  • a polymerization accelerator may be added as long as the effects of the present invention are not impaired.
  • the accelerator known ones can be used, and examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, and inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts thereof. It is done. Two or more of these may be used. Although it can select suitably as addition amount, it is preferable to add 1 mass part or less with respect to 100 mass parts of monomers (A).
  • additives for example, surfactants for controlling the particle size of polyamide fine particles, dispersants, modifying the properties of the polyamide fine particles, and improving the stability of the polymer (B) used.
  • Antioxidants, heat stabilizers, weathering agents, lubricants, pigments, dyes, plasticizers, antistatic agents, flame retardants and the like for improvement are included. Two or more of these may be used. Two or more different substances may be used for the purpose of modifying the monomer (A) or polyamide and for the purpose of modifying the polymer (B). Although it can select suitably as addition amount, it is preferable to add 1 mass part or less with respect to a total of 100 mass parts of a monomer (A) and a polymer (B).
  • the polyamide fine particles are homogeneously induced from the uniform solution, fine fine particles can be produced without performing stirring. However, even if stirring is performed to make the particle size control and particle size distribution more uniform. I do not care.
  • a stirring device a known device such as a stirring blade, a melt kneader, or a homogenizer can be used.
  • a stirring blade a propeller, paddle, flat, turbine, cone, anchor, screw, helical type, etc. Can be mentioned.
  • the stirring speed depends on the type and molecular weight of the polymer (B).
  • the stirring speed is 0 to 2,000 rpm. A range is preferable.
  • the lower limit of the stirring speed is more preferably 10 rpm or more, further preferably 30 rpm or more, particularly preferably 50 rpm or more, and the upper limit of the stirring speed is more preferably 1,600 rpm or less, further preferably 1,200 rpm or less, 800 rpm or less is particularly preferable.
  • a method of isolating after discharging the mixture at the time of the polymerization into the poor solvent of the polyamide fine particles, or the polyamide in the reaction vessel The method of isolating after adding the poor solvent of microparticles
  • a method of isolating by adding a poor solvent of polyamide fine particles to the reaction tank and a method of isolating by adding a poor solvent of polyamide fine particles to the reaction tank is more preferable.
  • a known method such as reduced pressure, pressure filtration, decantation, centrifugation, spray drying or the like can be appropriately selected.
  • the poor solvent for the polyamide fine particles is preferably a solvent that does not dissolve the polyamide but further dissolves the monomer (A) or the polymer (B).
  • a solvent can be appropriately selected, but alcohols such as methanol, ethanol and isopropanol, and water are preferable.
  • washing, isolation and drying of the polyamide fine particles can be carried out by known methods.
  • a cleaning method for removing the deposits and inclusions on the polyamide fine particles reslurry cleaning or the like can be used, and heating may be appropriately performed.
  • the solvent used in the washing is not limited as long as it does not dissolve the polyamide fine particles and dissolves the monomer (A) or the polymer (B).
  • methanol, ethanol, isopropanol, and water are usable. Water is most preferable.
  • Isolation can be appropriately selected from reduced pressure, pressure filtration, decantation, centrifugation, spray drying and the like. Drying is preferably carried out below the melting point of the polyamide fine particles, and may be reduced in pressure. Air drying, hot air drying, heat drying, reduced pressure drying, freeze drying and the like are selected.
  • Polyamide fine particles are produced by the above-described method. Particularly in the present invention, polyamide fine particles having a high crystallization temperature, which has been difficult until now, can be produced with a uniform particle diameter, a true sphere and a smooth surface. is there.
  • the high crystallization temperature polyamide constituting the polyamide fine particles of the present invention refers to a crystalline polyamide having a crystallization temperature of 150 ° C. or higher. Since the melting point and chemical resistance resulting from crystallinity increase and the polyamide becomes more heat resistant, the crystallization temperature of the polyamide is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and further preferably 180 ° C. or higher. . From the viewpoint of preventing the shape from becoming porous, the crystallization temperature of the polyamide is preferably 300 ° C. or less, more preferably 280 ° C. or less, and particularly preferably 260 ° C. or less.
  • polycaproamide polyamide 6
  • polyhexamethylene adipamide polyamide 66
  • polytetramethylene adipamide polyamide 46
  • polytetramethylene sebacamide polyamide 410
  • poly Pentamethylene adipamide polyamide 56
  • polypentamethylene sebamide polyamide 510
  • polyhexamethylene sebamide polyamide 610
  • polyhexamethylene dodecamide polyamide 612
  • polydecamethylene adipamide polyamide
  • polyamide 106 polydodecamethylene adipamide
  • polyamide 126 polyhexamethylene terephthalamide
  • polydecamethylene terephthalamide polyamide 10T
  • polycaproamide / polyhexamethylene adipamide copolymer Lyamide 6/66
  • polycaproamide polyamide 6
  • polyhexamethylene adipamide polyamide 66
  • polyhexamethylene sebamide polyamide 610
  • the number average particle diameter of the polyamide fine particles of the present invention is in the range of 0.1 to 100 ⁇ m. When the number average particle diameter exceeds 100 ⁇ m, the surface of the coating film prepared from the particles becomes inhomogeneous.
  • the number average particle diameter of the polyamide fine particles is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, further preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less. When the number average particle diameter is less than 0.1 ⁇ m, aggregation of particles occurs.
  • the number average particle diameter of the polyamide fine particles is preferably 0.3 ⁇ m or more, more preferably 0.7 ⁇ m or more, further preferably 1 ⁇ m or more, particularly preferably 2 ⁇ m or more, and most preferably 3 ⁇ m or more.
  • the particle size distribution index indicating the particle size distribution of the polyamide fine particles in the present invention is 3.0 or less. When the particle size distribution index exceeds 3.0, the fluidity is inferior in paint or cosmetic applications, and the uniformity of the coating film surface is impaired.
  • the particle size distribution index is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.3 or less, and most preferably 1.2 or less. The lower limit is theoretically 1.
  • the number average particle diameter of the polyamide fine particles can be calculated by specifying 100 particle diameters randomly from a scanning electron micrograph and calculating the arithmetic average thereof.
  • the maximum diameter of the particle is taken as the particle diameter.
  • it is measured at a magnification of at least 1,000 times, preferably at least 5,000 times.
  • the particle size distribution index is determined based on the following numerical conversion formula for the particle size value obtained above.
  • Di particle diameter of individual particles
  • n number of measurement 100
  • Dn number average particle diameter
  • Dv volume average particle diameter
  • PDI particle diameter distribution index
  • the polyamide fine particles of the present invention have a smooth surface in addition to a true spherical shape, and therefore can impart good slipperiness and fluidity to cosmetics and paints.
  • the sphericity indicating the sphericity of the polyamide fine particles is 90 or more. When the sphericity is less than 90, it is not possible to give a smoother feel in cosmetics and paint applications.
  • the sphericity is preferably 95 or more, more preferably 97 or more, and still more preferably 98 or more.
  • the upper limit is 100.
  • the sphericity of the polyamide fine particles is determined according to the following formula from the minor axis and major axis of 30 particles observed at random from a scanning electron micrograph.
  • S sphericity
  • a major axis
  • b minor axis
  • n number of measurements 30.
  • the smoothness of the polyamide fine particle surface can be expressed by the amount of the polyamide fine particles absorbing linseed oil. That is, the smoother the surface is, the finer particles have no pores on the surface, and the amount of linseed oil absorption that indicates the amount of linseed oil absorbed decreases.
  • the linseed oil absorption of the polyamide fine particles of the present invention is 100 mL / 100 g or less. When the linseed oil absorption amount of the polyamide fine particles exceeds 100 mL / 100 g, good fluidity cannot be imparted to cosmetics and paints.
  • the linseed oil absorption amount of the polyamide fine particles is preferably 90 mL / 100 g or less, more preferably 80 mL / 100 g or less, further preferably 70 mL / 100 g or less, and particularly preferably 60 mL / 100 g or less.
  • the lower limit of the linseed oil absorption is 0 mL / 100 g or more.
  • the oil absorption of linseed oil is measured according to Japanese Industrial Standard (JIS standard) JIS K 5101 “Pigment Test Method Refined Amani Oil Method”.
  • the smoothness of the surface can also be expressed by the BET specific surface area due to gas adsorption.
  • the smoother the surface the smaller the BET specific surface area.
  • it is preferably 10 m 2 / g or less, more preferably 5 m 2 / g or less, still more preferably 3 m 2 / g or less, and particularly preferably 1 m 2 / g or less.
  • it is 0.5 m 2 / g or less.
  • the BET specific surface area is measured according to Japanese Industrial Standard (JIS standard) JIS R 1626 (1996) “Method for measuring specific surface area by gas adsorption BET method”.
  • Average particle diameter and particle diameter distribution index The number average particle diameter of the polyamide fine particles was calculated by randomly identifying 100 particle diameters from a scanning electron micrograph and calculating the arithmetic average thereof. In the above photograph, when the shape is not a perfect circle, that is, when it is oval, the maximum diameter of the particle is taken as the particle diameter. In addition, the particle size distribution index was calculated based on the following numerical conversion formula for the particle size value obtained above.
  • Di particle diameter of individual particles
  • n number of measurement 100
  • Dn number average particle diameter
  • Dv volume average particle diameter
  • PDI particle diameter distribution index
  • S sphericity
  • a major axis
  • b minor axis
  • n number of measurements 30.
  • Linseed oil absorption amount According to Japanese Industrial Standard (JIS standard) JISK5101 “Pigment Test Method Purified Amani Oil Method”, about 100 mg of polyamide fine particles are precisely weighed on a watch glass, and refined linseed oil (Kanto Chemical Co., Ltd.) ) Is gradually added drop-by-drop with a burette, kneaded with a pallet knife, dripping and kneading is repeated until a sample lump is formed, and the point at which the paste becomes smooth is used as the end point. The oil absorption (mL / 100 g) was calculated from the amount of refined linseed oil.
  • Crystallization temperature and melting point of polyamide constituting polyamide fine particles Using a differential scanning calorimeter (DSCQ20) manufactured by TA Instruments, 30 ° C. higher than the endothermic peak indicating the melting point of the polyamide from 30 ° C. in a nitrogen atmosphere. The temperature was raised to a temperature of 20 ° C./min, held for 1 minute, and the peak of the exothermic peak that appeared when the temperature was cooled to 30 ° C. at a rate of 20 ° C./min was taken as the crystallization temperature. The endothermic peak when the temperature was further raised at 20 ° C./min after cooling was taken as the melting point.
  • the polyamide fine particle required for the measurement is about 8 mg.
  • the weight average molecular weight of the polyamide was calculated by using a gel permeation chromatography method and comparing it with a calibration curve using polymethyl methacrylate. A measurement sample was prepared by dissolving about 3 mg of polyamide fine particles in about 3 g of hexafluoroisopropanol.
  • Equipment Waters e-Alliance GPC system Column: Showa Denko HFIP-806M x 2 Mobile phase: 5 mmol / L sodium trifluoroacetate / hexafluoroisopropanol Flow rate: 1.0 ml / min Temperature: 30 ° C Detection: differential refractometer.
  • Molecular weight of polymer (B) The weight average molecular weight of the polymer (B) was calculated by comparing the weight average molecular weight with a calibration curve with polyethylene glycol using a gel permeation chromatography method. A measurement sample was prepared by dissolving about 3 mg of polymer (B) in about 6 g of water. Apparatus: LC-10A series manufactured by Shimadzu Corporation Column: TSKgelG3000PWXL manufactured by Tosoh Corporation Mobile phase: 100 mmol / L sodium chloride aqueous solution Flow rate: 0.8 ml / min Temperature: 40 ° C Detection: differential refractometer.
  • Example 1 In a 100 mL autoclave, 4 g of ⁇ -caprolactam (special grade made by Wako Pure Chemical Industries, SP value 19.5), polyethylene glycol (first grade polyethylene glycol 6,000, molecular weight 7,700, SP value made by Wako Pure Chemical Industries, Ltd.) 21.3) 6 g of water and 10 g of water for hydrolysis were sealed and replaced with nitrogen to 10 kg / cm 2 .
  • the system pressure was adjusted to 0.1 kg / cm 2 while releasing nitrogen, and then the temperature was raised to 240 ° C. In this case, after the pressure of the system it reached 10 kg / cm 2, pressure is controlled while steam was fine discharge pressure so as to maintain a 10 kg / cm 2.
  • the polymerization was started by releasing the pressure at a rate of 0.2 kg / cm 2 ⁇ min. At this point, the inner solution was uniformly transparent. While raising the temperature to 255 ° C. to reduce the pressure in the system until the 0 kg / cm 2, to complete the maintaining thermal polymerization while flowing 3 hours at the same time nitrogen becomes a 0 kg / cm 2. After the polymerization, the inner solution was suspended. Nitrogen was again charged to 10 kg / cm 2 and then cooled to room temperature. Water was added to the obtained solid and heated to 80 ° C. to dissolve the dissolved matter. The obtained slurry was filtered, and 40 g of water was added to the filtered product, followed by washing at 80 ° C.
  • the slurry liquid from which the agglomerate passed through a 200 ⁇ m sieve was removed was filtered again and the filtered product isolated was dried at 80 ° C. for 12 hours to obtain 2.8 g of powder. Moreover, there was no aggregate exceeding 200 ⁇ m.
  • the melting point of the obtained powder was 214 ° C. similar to that of polyamide 6, the crystallization temperature was 172 ° C., and the molecular weight was 38,000.
  • the polyamide 6 powder is in the form of true spherical particles, the number average particle size is 6.6 ⁇ m, the particle size distribution index is 1.08, the sphericity is 96, and the linseed oil absorption is 57 mL / 100 g, the BET specific surface area was 1.0 m 2 / g.
  • the SP value of polyamide 6 is 21.9.
  • FIG. 1 shows a scanning electron micrograph (magnification ⁇ 3000) of the true spherical polyamide 6 fine particles. Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Example 2 Polymerization was performed in the same manner as in Example 1 except that 5 g of ⁇ -caprolactam and 5 g of polyethylene glycol (first grade polyethylene glycol 6,000 manufactured by Wako Pure Chemical Industries, Ltd.) were changed to obtain 0.7 g of powder. . It was a homogeneous solution at the start of polymerization and a suspension after polymerization. The obtained powder had a melting point of 216 ° C. similar to that of polyamide 6, a crystallization temperature of 169 ° C., and a molecular weight of 44,100.
  • the polyamide 6 powder is a true sphere and has a smooth surface fine particle shape, the number average particle size is 12.9 ⁇ m, the particle size distribution index is 1.76, the sphericity is 95, and the linseed oil absorption is It was 54 mL / 100 g.
  • a scanning electron micrograph (magnification x1000) of the true spherical polyamide 6 fine particles is shown in FIG. Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Example 3 Polymerization was performed in the same manner as in Example 1 except that 2 g of ⁇ -caprolactam and 8 g of polyethylene glycol (first grade polyethylene glycol 6,000 manufactured by Wako Pure Chemical Industries, Ltd.) were changed to obtain 1.5 g of powder. . It was a homogeneous solution at the start of polymerization and a suspension after polymerization. The melting point of the obtained powder was 213 ° C. similar to that of polyamide 6, the crystallization temperature was 172 ° C., and the molecular weight was 26,800.
  • the polyamide 6 powder has a spherical shape with a smooth sphere, a number average particle size of 5.3 ⁇ m, a particle size distribution index of 1.24, a sphericity of 95, and linseed oil absorption is It was 59 mL / 100 g.
  • Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Example 4 Polymerization is carried out in the same manner as in Example 1 except that the molecular weight is changed to polyethylene glycol having a different molecular weight (first grade polyethylene glycol 20,000, molecular weight 18,600, SP value 21.3, manufactured by Wako Pure Chemical Industries, Ltd.). 3.3g was obtained. After the polymerization, it was a homogeneous solution, and was a suspension solution at the end of the polymerization. The obtained powder had a melting point of 211 ° C. similar to that of polyamide 6, a crystallization temperature of 170 ° C., and a molecular weight of 35,600.
  • the polyamide 6 powder has a true spherical shape with a smooth surface, a number average particle size of 6.1 ⁇ m, a particle size distribution index of 1.23, a sphericity of 92, and linseed oil absorption.
  • Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Example 5 Polymerization was carried out in the same manner as in Example 1 except that the molecular weight was changed to polyethylene glycol having a different molecular weight (primary polyethylene glycol 35,000 manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 31,000, SP value 21.3). 2.1 g was obtained. It was a homogeneous solution at the start of polymerization and a suspension after polymerization. The obtained powder had a melting point of 210 ° C. similar to that of polyamide 6, a crystallization temperature of 175 ° C., and a molecular weight of 32,500.
  • the polyamide 6 powder is a true sphere and has a smooth surface fine particle shape, the number average particle size is 3.5 ⁇ m, the particle size distribution index is 1.15, the sphericity is 93, and the linseed oil absorption amount was 59 mL / 100 g.
  • Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Polymerization was carried out in the same manner as in Example 1 except that the molecular weight was changed to polyethylene glycol having a different molecular weight (primary polyethylene glycol 2,000, molecular weight 2,300, SP value 21.3, manufactured by Wako Pure Chemical Industries, Ltd.). 2.3 g was obtained.
  • the polyamide 6 powder is a true sphere and has a smooth surface fine particle shape, the number average particle size is 6.1 ⁇ m, the particle size distribution index is 1.34, the sphericity is 93, and the linseed oil absorption is Was 53 mL / 100 g. Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Example 7 Polymerization was carried out in the same manner as in Example 1 except that polyethylene glycol was changed to polypropylene glycol (first grade polypropylene glycol 2,000, molecular weight 3,600, SP value 18.7, manufactured by Wako Pure Chemical Industries, Ltd.). 2.3 g was obtained. It was a homogeneous solution at the start of polymerization and a suspension after polymerization. The obtained powder had a melting point of 216 ° C. similar to that of polyamide 6, a crystallization temperature of 170 ° C., and a molecular weight of 38,000.
  • the polyamide 6 powder is a true sphere and has a smooth surface fine particle shape, the number average particle size is 21.5 ⁇ m, the particle size distribution index is 1.92, the sphericity is 91, and the linseed oil absorption amount was 65 mL / 100 g.
  • Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Example 8 Polymerization was performed in the same manner as in Example 1 except that polyethylene glycol was changed to polytetramethylene glycol (primary polytetramethylene glycol 2,000, molecular weight 7,500, SP value 17.9 manufactured by Wako Pure Chemical Industries, Ltd.). And 2.3 g of powder was obtained. It was a homogeneous solution at the start of polymerization and a suspension after polymerization. The obtained powder had a melting point of 214 ° C. similar to that of polyamide 6, a crystallization temperature of 169 ° C., and a molecular weight of 40,200.
  • the polyamide 6 powder is a true sphere and has a smooth surface fine particle shape, the number average particle size is 31.5 ⁇ m, the particle size distribution index is 2.76, the sphericity is 90, and the linseed oil absorption amount was 63 mL / 100 g.
  • Table 1 shows the properties of the obtained polyamide 6 fine particles.
  • Example 9 In a 100 mL autoclave, 1.7 g of adipic acid (Tokyo Chemical Industry Co., Ltd., SP value 25.4), hexamethylenediamine 50% aqueous solution 2.2 g (Tokyo Chemical Industry Co., Ltd., SP value 19.2), polyethylene glycol (Wako Pure Chemical Industries, Ltd., first grade polyethylene glycol 20,000, molecular weight 18,600) 6 g and 2.6 g of water as a solvent were added and sealed, and then replaced with nitrogen to 10 kg / cm 2 . The system pressure was adjusted to 0.1 kg / cm 2 while releasing nitrogen, and then the temperature was raised to 260 ° C.
  • the obtained powder had a melting point of 267 ° C. similar to that of polyamide 66, a crystallization temperature of 211 ° C., and a molecular weight of 73,600.
  • the polyamide 66 powder is spherical and has a smooth surface fine particle shape by scanning electron microscope observation, the number average particle size is 6.5 ⁇ m, the particle size distribution index is 1.60, the sphericity is 91, and linseed oil absorption The amount was 56 mL / 100 g.
  • FIG. 3 shows a scanning electron micrograph (magnification ⁇ 1500) of the true spherical polyamide 66 fine particles.
  • the SP value of polyamide 66 is 20.6.
  • the properties of the obtained polyamide 66 fine particles are shown in Table 2.
  • Example 10 4 g of aminohexanoic acid (manufactured by Wako Pure Chemical Industries, SP value 17.5), 6 g of polyethylene glycol (primary polyethylene glycol 6,000 manufactured by Wako Pure Chemical Industries, Ltd.) and 10 g of water as a solvent are added to a 100 mL autoclave. A homogeneous solution was sealed after formation and replaced with nitrogen to 10 kg / cm 2 . The system pressure was adjusted to 0.1 kg / cm 2 while releasing nitrogen, and then the temperature was raised to 240 ° C. In this case, after the pressure of the system it reached 10 kg / cm 2, pressure is controlled while steam was fine discharge pressure so as to maintain a 10 kg / cm 2.
  • the polymerization was started by releasing the pressure at a rate of 0.2 kg / cm 2 ⁇ min. While raising the temperature to 255 ° C., the pressure in the system was lowered to 0, and at the same time, heating was maintained while flowing nitrogen for 3 hours to complete the polymerization. After the polymerization, the inner solution was suspended. Nitrogen was again charged to 10 kg / cm 2 and then cooled to room temperature. Water was added to the obtained solid and heated to 80 ° C. to dissolve the dissolved matter. The obtained slurry was filtered, and 40 g of water was added to the filtered product, followed by washing at 80 ° C.
  • the obtained powder had a melting point of 216 ° C. similar to that of polyamide 6, a crystallization temperature of 170 ° C., and a molecular weight of 21,000.
  • the polyamide 6 powder has a spherical fine particle shape, the number average particle size is 13.1 ⁇ m, the particle size distribution index is 1.54, the sphericity is 92, and the linseed oil absorption is 60 mL / 100 g.
  • the properties of the obtained polyamide 6 fine particles are shown in Table 2.
  • Example 11 Implemented except that aminohexanoic acid was changed to aminododecanoic acid (manufactured by Wako Pure Chemical Industries, Ltd., SP value 17.2), polyethylene glycol having a different molecular weight (primary polyethylene glycol 20,000 manufactured by Wako Pure Chemical Industries, Ltd.) Polymerization was performed in the same manner as in Example 10 to obtain 0.8 g of powder. A uniform solution was formed from the time when the temperature was raised to 100 ° C. or higher, and the suspension was a suspension after polymerization. The melting point of the obtained powder was 173 ° C. similar to that of polyamide 12, the crystallization temperature was 139 ° C., and the molecular weight was 110,000.
  • the polyamide 12 powder has a true spherical shape and a smooth surface fine particle shape, the number average particle size is 6.6 ⁇ m, the particle size distribution index is 1.37, the sphericity is 94, and the linseed oil absorption is It was 54 mL / 100 g.
  • FIG. 4 shows a scanning electron micrograph (magnification ⁇ 1000) of the true spherical polyamide 12 fine particles.
  • Table 2 shows the properties of the obtained polyamide 12 fine particles.
  • Example 12 Polymerization was performed in the same manner as in Example 11 except that 2 g of aminododecanoic acid and 8 g of polyethylene glycol were changed to obtain 1.2 g of powder.
  • the melting point of the obtained powder was 175 ° C. similar to that of polyamide 12, the crystallization temperature was 136 ° C., and the molecular weight was 50,000.
  • the polyamide 12 powder has a spherical shape and a fine particle shape with a smooth surface.
  • the number average particle size is 6.0 ⁇ m
  • the particle size distribution index is 1.30
  • the sphericity is 96
  • the linseed oil absorption is It was 58 mL / 100g.
  • Table 2 shows the properties of the obtained polyamide 12 fine particles.
  • Example 1 Example 1 except that polyethylene glycol was changed to dimethyl silicone oil (KF-96H, 10,000 cs, molecular weight 88,400, SP value 14.5, manufactured by Shin-Etsu Chemical Co., Ltd.), and water at the time of washing was changed to toluene. Polymerization was carried out by the method. It separated into two phases at the start of polymerization, and remained coarsely separated into two phases of silicone and polyamide after polymerization. Washing was performed using toluene, but 3.2 g of polyamide aggregates were recovered over 200 ⁇ m, and no particles were obtained.
  • KF-96H 10,000 cs, molecular weight 88,400, SP value 14.5, manufactured by Shin-Etsu Chemical Co., Ltd.
  • FIG. 5 shows a scanning electron micrograph (magnification ⁇ 1000) of the amorphous polyamide 6 fine particles.
  • the properties of the obtained polyamide 6 fine particles are shown in Table 2.
  • the fine sphere surface smooth and narrow particle size distribution of the polyamide fine particles of the present invention has a high crystallization temperature and high heat resistance and chemical resistance inherent to the high crystallization temperature polyamide, and a spherical and smooth surface with a narrow particle size distribution. Therefore, it also has slipperiness, paint, adhesive, ink, toner light diffusing agent, liquid crystal spacer, matting agent, polymer alloy additive, various catalyst carriers, chromatography carriers, automobile parts, It can be suitably used for aircraft parts, electronic parts, cosmetic additives and medical carriers.
  • the heat resistance derived from a high crystallization temperature, a spherical and smooth surface form, and a uniform particle diameter can be applied to highly functional paints such as severe conditions that cannot be used conventionally.
  • the amide group concentration in the polyamide is increased, so that the moisture retention is increased, and it is possible to achieve both a smooth and uniform feel and a moist feeling due to the true spherical shape and uniform particle size.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyamides (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
PCT/JP2018/017616 2017-05-12 2018-05-07 ポリアミド微粒子の製造方法およびポリアミド微粒子 WO2018207728A1 (ja)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US16/606,837 US11485822B2 (en) 2017-05-12 2018-05-07 Method of producing polyamide fine particles, and polyamide fine particles
CN201880030995.2A CN110612320B (zh) 2017-05-12 2018-05-07 聚酰胺微粒的制造方法及聚酰胺微粒
KR1020197029952A KR102538062B1 (ko) 2017-05-12 2018-05-07 폴리아미드 미립자의 제조 방법 및 폴리아미드 미립자
RU2019140599A RU2771710C2 (ru) 2017-05-12 2018-05-07 Способ получения мелких частиц полиамида и мелкие частицы полиамида
EP18798029.7A EP3623411A4 (en) 2017-05-12 2018-05-07 PROCESS FOR PRODUCING FINE PARTICLES FROM POLYAMIDE AND FINE PARTICLES FROM POLYAMIDE
JP2018525495A JP6558498B2 (ja) 2017-05-12 2018-05-07 ポリアミド微粒子の製造方法
US17/955,169 US11807717B2 (en) 2017-05-12 2022-09-28 Method of producing polyamide fine particles, and polyamide fine particles

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017-095286 2017-05-12
JP2017095286 2017-05-12
JP2018-014437 2018-01-31
JP2018014437 2018-01-31

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US16/606,837 A-371-Of-International US11485822B2 (en) 2017-05-12 2018-05-07 Method of producing polyamide fine particles, and polyamide fine particles
US17/955,169 Division US11807717B2 (en) 2017-05-12 2022-09-28 Method of producing polyamide fine particles, and polyamide fine particles

Publications (2)

Publication Number Publication Date
WO2018207728A1 true WO2018207728A1 (ja) 2018-11-15
WO2018207728A9 WO2018207728A9 (ja) 2019-03-21

Family

ID=64104749

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/017616 WO2018207728A1 (ja) 2017-05-12 2018-05-07 ポリアミド微粒子の製造方法およびポリアミド微粒子

Country Status (6)

Country Link
US (2) US11485822B2 (zh)
EP (1) EP3623411A4 (zh)
JP (2) JP6558498B2 (zh)
KR (1) KR102538062B1 (zh)
CN (1) CN110612320B (zh)
WO (1) WO2018207728A1 (zh)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020095702A1 (ja) * 2018-11-09 2020-05-14 東レ株式会社 ポリアミド微粒子の製造方法、およびポリアミド微粒子
WO2021090768A1 (ja) * 2019-11-05 2021-05-14 東レ株式会社 ３次元造形物を製造するためのポリマー粉末、ポリマー粉末を用いて粉末床溶融結合方式によって３次元造形物を製造する方法、および３次元造形物
WO2021131740A1 (ja) 2019-12-26 2021-07-01 東レ株式会社 プリプレグ
WO2021132091A1 (ja) 2019-12-23 2021-07-01 東レ株式会社 熱硬化性樹脂組成物、熱硬化性樹脂硬化物、プリプレグ及び繊維強化複合材料
WO2022004586A1 (ja) 2020-06-30 2022-01-06 東レ株式会社 繊維強化複合材料およびプリプレグの製造方法
WO2022181633A1 (ja) 2021-02-25 2022-09-01 東レ株式会社 ポリマー粉末およびその製造方法、並びに３次元造形物の製造方法
WO2022181634A1 (ja) 2021-02-25 2022-09-01 東レ株式会社 樹脂粉粒体を用いた３次元造形物の製造方法、３次元造形物、並びに樹脂粉粒体
WO2023008357A1 (ja) 2021-07-27 2023-02-02 東レ株式会社 炭素繊維強化複合材料
WO2023074733A1 (ja) 2021-10-27 2023-05-04 東レ株式会社 炭素繊維強化複合材料
WO2024043029A1 (ja) * 2022-08-23 2024-02-29 東レ株式会社 ３次元造形物を製造するためのポリマー粒子およびポリマー粒子組成物、およびポリマー粒子の製造方法、ならびに３次元造形物とその製造方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102309284B1 (ko) * 2018-08-03 2021-10-06 주식회사 엘지에너지솔루션 고분자 솔루션의 미용해물 측정법
CN113337105B (zh) * 2020-03-02 2022-09-23 中国科学院化学研究所 一种聚合物粉体及其制备方法
CN113354942B (zh) * 2020-03-02 2022-10-18 中国科学院化学研究所 一种聚合物粉体及其制备方法
CN112876674A (zh) * 2021-03-17 2021-06-01 滨州学院 一种原位水解开环制备聚酰胺微球的方法
WO2023284585A1 (zh) * 2021-07-13 2023-01-19 东丽先端材料研究开发（中国）有限公司 一种聚酰胺微粒及其制备方法
CN114621485B (zh) * 2022-04-12 2023-04-07 滨州学院 树莓状多孔聚酰胺微球制备方法及制备的聚酰胺材料
CN115093584A (zh) * 2022-07-22 2022-09-23 贵州省冶金化工研究所 一种选择性激光打印用均匀球化尼龙粉末制备方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6040134A (ja) 1983-08-13 1985-03-02 Showa Denko Kk ポリアミド樹脂微粒子の製造法
JPS61181826A (ja) 1985-01-30 1986-08-14 エルフ　アトケム　ソシエテ　アノニム ポリアミド粉末の製造方法
JPH0873602A (ja) 1994-09-09 1996-03-19 Shinto Paint Co Ltd ポリアミド粉体の製造方法
JPH10316750A (ja) 1997-03-18 1998-12-02 Ube Ind Ltd 球状ポリアミドおよびその製法
JP2000248028A (ja) * 1999-03-03 2000-09-12 Mitsubishi Chemicals Corp 水性分散液及びその製造方法
JP2002080629A (ja) 2000-06-14 2002-03-19 Ube Ind Ltd ポリアミド多孔質球状粒子およびその製造方法
JP2003171682A (ja) * 2001-12-10 2003-06-20 Shinto Fine Co Ltd 滑 剤
JP2007119632A (ja) * 2005-10-28 2007-05-17 Toray Ind Inc 新規ポリアミド微粒子およびそれを含む化粧品
JP2010053272A (ja) 2008-08-29 2010-03-11 Ube Ind Ltd 紫外線防除機能を有する複合化ポリアミド多孔質微粒子およびその製造方法
WO2012161174A1 (ja) * 2011-05-25 2012-11-29 独立行政法人産業技術総合研究所 物性が改質された２－ピロリドンの重合体又は共重合体及びその製造方法
WO2016102879A1 (fr) * 2014-12-22 2016-06-30 Arkema France Fabrication de poudres de polyamide par aminolyse d'ester
JP2016186068A (ja) * 2015-03-19 2016-10-27 株式会社リコー ポリアミド粒子及びその製造方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2742440A (en) * 1952-02-26 1956-04-17 Polymer Corp Method of preparing finely divided polyamides
US3446782A (en) * 1965-04-14 1969-05-27 Toray Industries Method of manufacture of powdery synthetic linear polyamides
FR2856692B1 (fr) * 2003-06-26 2005-08-05 Rhodia Polyamide Intermediates Procede de preparation de particules spheriques a base de polyamide.
JP5024672B2 (ja) * 2005-02-02 2012-09-12 宇部興産株式会社 多孔質球状ポリアミド粒子の製造方法
JP2006328208A (ja) * 2005-05-26 2006-12-07 Daicel Degussa Ltd 真球状熱可塑性樹脂微粒子の製造法
JP5073214B2 (ja) * 2006-03-13 2012-11-14 ダイセル・エボニック株式会社 樹脂粒子の製造方法及び樹脂粒子
JP5029313B2 (ja) * 2006-11-21 2012-09-19 東レ株式会社 ポリカプロアミド樹脂複合微粒子
JP5648740B2 (ja) * 2012-02-15 2015-01-07 東レ株式会社 複合ポリアミド微粒子およびその製造方法
US9676936B2 (en) * 2013-01-28 2017-06-13 Toray Industries, Inc. Prepreg, fiber-reinforced composite material, and thermoplastic resin particles
CN104045826B (zh) * 2014-06-25 2016-03-30 江苏科技大学 一种聚酰胺微球的环保型制备方法
CN105622932B (zh) * 2014-11-07 2019-12-06 合肥杰事杰新材料股份有限公司 一种纳米尼龙微球及其制备方法
CN107108906B (zh) * 2014-12-24 2020-01-10 东丽株式会社 聚酰胺微粒
US10138344B2 (en) 2015-03-19 2018-11-27 Ricoh Company, Ltd. Particulate polyamide, and method for preparing the particulate polyamide

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6040134A (ja) 1983-08-13 1985-03-02 Showa Denko Kk ポリアミド樹脂微粒子の製造法
JPS61181826A (ja) 1985-01-30 1986-08-14 エルフ　アトケム　ソシエテ　アノニム ポリアミド粉末の製造方法
JPH0873602A (ja) 1994-09-09 1996-03-19 Shinto Paint Co Ltd ポリアミド粉体の製造方法
JPH10316750A (ja) 1997-03-18 1998-12-02 Ube Ind Ltd 球状ポリアミドおよびその製法
JP2000248028A (ja) * 1999-03-03 2000-09-12 Mitsubishi Chemicals Corp 水性分散液及びその製造方法
JP2002080629A (ja) 2000-06-14 2002-03-19 Ube Ind Ltd ポリアミド多孔質球状粒子およびその製造方法
JP2003171682A (ja) * 2001-12-10 2003-06-20 Shinto Fine Co Ltd 滑 剤
JP2007119632A (ja) * 2005-10-28 2007-05-17 Toray Ind Inc 新規ポリアミド微粒子およびそれを含む化粧品
JP2010053272A (ja) 2008-08-29 2010-03-11 Ube Ind Ltd 紫外線防除機能を有する複合化ポリアミド多孔質微粒子およびその製造方法
WO2012161174A1 (ja) * 2011-05-25 2012-11-29 独立行政法人産業技術総合研究所 物性が改質された２－ピロリドンの重合体又は共重合体及びその製造方法
WO2016102879A1 (fr) * 2014-12-22 2016-06-30 Arkema France Fabrication de poudres de polyamide par aminolyse d'ester
JP2016186068A (ja) * 2015-03-19 2016-10-27 株式会社リコー ポリアミド粒子及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
D.W. VAN KREVELEN: "Properties of Polymers", 2009, ELSEVIER SCIENCE, pages: 215

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020095702A1 (ja) * 2018-11-09 2020-05-14 東レ株式会社 ポリアミド微粒子の製造方法、およびポリアミド微粒子
JP6702516B1 (ja) * 2018-11-09 2020-06-03 東レ株式会社 ポリアミド微粒子の製造方法、およびポリアミド微粒子
US11685813B2 (en) 2018-11-09 2023-06-27 Toray Industries, Inc. Method of producing polyamide fine particles, and polyamide fine particles
WO2021090768A1 (ja) * 2019-11-05 2021-05-14 東レ株式会社 ３次元造形物を製造するためのポリマー粉末、ポリマー粉末を用いて粉末床溶融結合方式によって３次元造形物を製造する方法、および３次元造形物
WO2021132091A1 (ja) 2019-12-23 2021-07-01 東レ株式会社 熱硬化性樹脂組成物、熱硬化性樹脂硬化物、プリプレグ及び繊維強化複合材料
WO2021131740A1 (ja) 2019-12-26 2021-07-01 東レ株式会社 プリプレグ
WO2022004586A1 (ja) 2020-06-30 2022-01-06 東レ株式会社 繊維強化複合材料およびプリプレグの製造方法
WO2022181633A1 (ja) 2021-02-25 2022-09-01 東レ株式会社 ポリマー粉末およびその製造方法、並びに３次元造形物の製造方法
WO2022181634A1 (ja) 2021-02-25 2022-09-01 東レ株式会社 樹脂粉粒体を用いた３次元造形物の製造方法、３次元造形物、並びに樹脂粉粒体
WO2023008357A1 (ja) 2021-07-27 2023-02-02 東レ株式会社 炭素繊維強化複合材料
WO2023074733A1 (ja) 2021-10-27 2023-05-04 東レ株式会社 炭素繊維強化複合材料
WO2024043029A1 (ja) * 2022-08-23 2024-02-29 東レ株式会社 ３次元造形物を製造するためのポリマー粒子およびポリマー粒子組成物、およびポリマー粒子の製造方法、ならびに３次元造形物とその製造方法

Also Published As

Publication number Publication date
KR102538062B1 (ko) 2023-05-30
RU2019140599A3 (zh) 2021-07-01
US20230034929A1 (en) 2023-02-02
CN110612320A (zh) 2019-12-24
WO2018207728A9 (ja) 2019-03-21
EP3623411A4 (en) 2021-01-20
JP6558498B2 (ja) 2019-08-14
US20200048413A1 (en) 2020-02-13
JP2019167545A (ja) 2019-10-03
JPWO2018207728A1 (ja) 2019-06-27
RU2019140599A (ru) 2021-06-15
US11807717B2 (en) 2023-11-07
KR20190141664A (ko) 2019-12-24
JP6756390B2 (ja) 2020-09-16
CN110612320B (zh) 2022-04-15
US11485822B2 (en) 2022-11-01
EP3623411A1 (en) 2020-03-18

Similar Documents

Publication Publication Date Title
JP6558498B2 (ja) ポリアミド微粒子の製造方法
CN107108906B (zh) 聚酰胺微粒
TWI631150B (zh) 聚苯硫微粒子、含有其之分散液、及聚苯硫微粒子之製造方法
JP6780795B2 (ja) ポリアミド微粒子
WO2021090768A1 (ja) ３次元造形物を製造するためのポリマー粉末、ポリマー粉末を用いて粉末床溶融結合方式によって３次元造形物を製造する方法、および３次元造形物
JP5821213B2 (ja) ポリフェニレンサルファイド樹脂微粒子分散液の製造方法
JP4093142B2 (ja) ポリアミド多孔質粒子の製造方法
WO2022181633A1 (ja) ポリマー粉末およびその製造方法、並びに３次元造形物の製造方法
RU2771710C2 (ru) Способ получения мелких частиц полиамида и мелкие частицы полиамида
JP4528482B2 (ja) ポリアミド粒子及びその製造方法
JP2021091861A (ja) ポリアミド微粒子の製造方法
CN116887972A (zh) 聚合物粉末及其制造方法以及3维造型物的制造方法
WO2024043029A1 (ja) ３次元造形物を製造するためのポリマー粒子およびポリマー粒子組成物、およびポリマー粒子の製造方法、ならびに３次元造形物とその製造方法
WO2023284585A1 (zh) 一种聚酰胺微粒及其制备方法
JP2021070710A (ja) 樹脂粒子、および樹脂粒子の製造方法
JP2021070709A (ja) 樹脂粒子、および樹脂粒子の製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018525495

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18798029

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197029952

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2018798029

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2018798029

Country of ref document: EP

Effective date: 20191212